4-([1,4'-Bipiperidin]-1'-yl)-2-chloro-7-(2,6-dichlorobenzyl)-7H-pyrrolo[2,3-d]pyrimidine 12a. White
solid, yield 65 %, Mp 94-95 °C. 1H NMR (400 MHz, CDCl3) δ 7.24 (d, J = 8.0 Hz, 2H, H3’ and H5’), 7.15 –
7.11 (m, 1H, H4’), 6.42 (d, J = 3.7 Hz, 1H, H6), 6.23 (d, J = 3.7 Hz, 1H, H5), 5.46 (s, 2H, CH2), 4.66 (d, J =
13.3 Hz, 2H, H2’’ and H6’’), 2.92 (t, J = 12.1 Hz, 2H, H2’’ and H6’’), 2.58 (t, J = 10.9 Hz, 1H, H4’’), 2.47
(br, 4H, 2 x H8’’ and 2 x H12’’), 1.88 (d, J = 12.2 Hz, 2H, H9’’ and H11’’), 1.63 – 1.43 (m, 6H, 2 x H3’’, 2 x
H5’’, H9’’ and H11’’), 1.36 – 1.22 (m, 2H, 2 x H10’’). 13C NMR (101 MHz, CDCl3) δ 157.06, 153.31, 152.52
(2C), 137.04, 131.58, 130.44, 128.72 (2C), 121.99, 101.48, 101.20, 62.82, 50.12 (2C), 45.42, 43.39 (2C),
27.56 (2C), 25.69 (2C), 24.32. HRMS m/z 478.1327 [M+H+] (calcd. for C23H26Cl3N5, 478.1265).
4-([1,4'-Bipiperidin]-1'-yl)-7-(4-chlorobenzyl)-7H-pyrrolo[2,3-d]pyrimidine 9b. Brown solid, yield 47
%, Mp 103-104 °C. 1H NMR (400 MHz, CDCl3) δ 8.45 (s, 1H, H2), 7.36 (d, J = 8.1 Hz, 2H, H3’ and H5’),
7.22 (d, J = 8.0 Hz, 2H, H2’ and H6’), 7.00 (d, J = 3.1 Hz, 1H, H6), 6.60 (d, J = 3.2 Hz, 1H, H5), 5.45 (s, 2H,
CH2), 4.97 (d, J = 13.0 Hz, 2H, H2’’ and H6’’), 3.19 (t, J = 12.5 Hz, 2H, H2’’ and H6’’), 3.00 (t, J = 11.1 Hz,
1H, H4’’), 2.83 (br, 4H, 2 x H8’’ and 2 x H12’’), 2.22 (d, J = 11.6 Hz, 2H, H9’’ and H11’’), 1.94 – 1.77 (m,
6H, 2 x H3’’, 2 x H5’’, H9’’ and H11’’), 1.61 (s, 2H, 2 x H10’’). 13C NMR (101 MHz, CDCl3) δ 156.74, 151.44
(2C), 135.87, 133.56, 128.88 (2C), 128.79 (2C), 123.38, 103.05, 101.41, 63.28, 50.02 (2C), 47.30, 45.30
(2C), 27.23 (2C), 25.01 (2C), 23.90. HRMS m/z 410.2106 [M+H+] (calcd. for C23H28ClN5, 410.2048).
4-([1,4'-Bipiperidin]-1'-yl)-7-(4-fluorobenzyl)-7H-pyrrolo[2,3-d]pyrimidine 10b. Brown solid, yield 58
%, Mp 118-120 °C. 1H NMR (400 MHz, CDCl3) δ 8.61 (s, 1H, H2), 7.42 (dd, J = 8.2, 5.5 Hz, 2H, H3’ and
H5’), 7.23 (t, J = 8.6 Hz, 2H, H2’ and H6’), 7.15 (d, J = 3.6 Hz, 1H, H6), 6.74 (d, J = 3.6 Hz, 1H, H5), 5.60
(s, 2H, CH2), 5.11 (d, J = 13.3 Hz, 2H, H2’’ and H6’’), 3.33 (t, J = 12.2 Hz, 2H, H2’’ and H6’’), 3.07 (t, J =
11.5 Hz, 1H, H4’’), 2.93 (br, 4H, 2 x H8’’ and 2 x H12’’), 2.34 (d, J = 12.0 Hz, 2H, H9’’ and H11’’), 2.06 –
1.84 (m, 6H, 2 x H3’’, 2 x H5’’, H9’’ and H11’’), 1.75 (d, J = 4.9 Hz, 2H, 2 x H10’’). 13C NMR (101 MHz,
CDCl3) δ 162.30 (d, JCF = 246.1 Hz), 156.79, 151.46, 151.42, 133.16 (d, JCF = 3.2 Hz), 129.19 (d, JCF = 8.2
Hz, 2C), 123.27, 115.61 (d, JCF = 21.6 Hz, 2C), 103.05, 101.36, 63.20, 50.08 (2C), 47.24, 45.40 (2C), 27.43
(2C), 25.34 (2C), 24.11. 19F NMR (376 MHz, CDCl3) δ -114.67. HRMS m/z 394.2402 [M+H+] (calcd. for
C23H28FN5, 394.2346).
4-((4-([1,4'-Bipiperidin]-1'-yl)-7H-pyrrolo[2,3-d]pyrimidin-7-yl)methyl)benzonitrile 11b. Brown solid,
yield 52 %, Mp 101-103 °C. 1H NMR (400 MHz, CDCl3) δ 8.32 (s, 1H, H2), 7.57 (d, J = 8.1 Hz, 2H, H3’ and
H5’), 7.22 (d, J = 8.0 Hz, 2H, H2’ and H6’), 6.90 (d, J = 3.5 Hz, 1H, H6), 6.53 (d, J = 3.5 Hz, 1H, H5), 5.43
(s, 2H, CH2), 4.84 (d, J = 13.2 Hz, 2H, H2’’ and H6’’), 3.08 (t, J = 12.4 Hz, 2H, H2’’ and H6’’), 2.77 (t, J =
11.3 Hz, 1H, H4’’), 2.68 – 2.57 (br, 4H, 2 x H8’’ and 2 x H12’’), 2.06 (d, J = 11.9 Hz, 2H, H9’’ and H11’’),
1.77 – 1.56 (m, 6H, 2 x H3’’, 2 x H5’’, H9’’ and H11’’), 1.47 (s, 2H, 2 x H10’’). 13C NMR (101 MHz, CDCl3)
δ 156.83, 151.69, 151.52, 142.84, 132.56 (2C), 127.77 (2C), 123.15, 118.55, 111.61, 102.99, 101.94,
15